Kolmogorov-Smirnov isometries of the space of generalized distribution functions

In this paper we describe the structure of surjective isometries of the space of all generalized probability distribution functions on ? with respect to the Kolmogorov-Smirnov metric.     

Occupation Time of Exclusion Processes with Conductances

We obtain the fluctuations for the occupation time of one-dimensional symmetric exclusion processes with speed change, where the transition rates (conductances) are driven by a general function \(W\) . The approach does not require sharp bounds on the spectral gap of the system nor the jump rates to be bounded from above or below. We present some examples and for one of them, we observe that the fluctuations of the current are trivial, but the fluctuations of the occupation time are given by a fractional Brownian Motion. This shows that, in general, the fluctuations of the current and of the occupation time are not of same order.     

Roadmap to spline-fitting potentials in high dimensions

The use of the theory of splines to approximate the potential energy surface in molecular dynamics is examined. It is envisaged that such an approximation should be able to accurately capture the potentials’ behavior and be computationally cost effective, both for one-dimensional and $n$ -dimensional problems with $n$ arbitrary. In this regard, the problem of dimensionality is pinpointed, with shape-preserving splines emerging as a viable alternative for fitting surfaces in multidimensional spaces. An algorithm is also presented to allow the use of non-uniform meshes with high accuracy fitting and less interpolation points.     

On an exact classical wave solution of the Einstein equations

The J. Scherk and J. H. Schwarz generalization of a Peres solution is shown to be the Peres solution in a different system of coordinates.     

n -Heptane and methylcyclohexane transformation over a HMCM-22 zeolite. Origin of the features typical of large-or of medium-pore zeolites

The main features of methylcyclohexane (mch) and n-heptane (n-C₇) transformation at 350°C were compared for fresh samples of HMWW, HMFI and HFAU zeolites. With both reactions, the behavior of HMWW was between those of the medium HMFI and large pore HFAU zeolites. Thus, the values of turnover frequency (TOF) and of the TOF_mch/n-C7 ratio were similar with HMWW and HMFI and much higher with HFAU. In contrast, small differences were found between product distributions over HMWW and HFAU but large differences between HMWW and HMFI. These observations can be explained by alkane transformation in the large supercages with 10-MR apertures of HMWW: the narrow apertures limit diffusion of the mch within the supercages, but not the diffusion of the products which are therefore typical of the transformation within large cages hence without any steric limitation.     

Unusual coordination environment for barium cations in ion recognition conducting poly[Ni(salen)(receptor)] films

[Ni( salen)] complexes bearing different crown ether receptors were electropolymerized to give films whose voltammetric signatures responded to Ba2+. In line with DFT calculations, X-ray absorption spectroscopy (XAS) near the Ni K-edge showed the nickel local environment in the monomers and their corresponding polymers (in the presence or absence of barium) to be identical. However, the expectation of crown size-dependent barium local environment (based on geometry and donor atom availability) was not found. XAS near the Ba K-edge showed that Ba2+ in the films coordinated to only two oxygen donors, irrespective of crown size. This surprisingly low coordination number (compared to solution species) is accompanied by a higher barium/crown ratio than the anticipated 1:1 stoichiometry. The implications of these effects for design and performance of sensors based on metal ion recognition chemistry are discussed.     

On the localization of water-soluble porphyrins in micellar systems evaluated by static and time-resolved frequency-domain fluorescence techniques

Fluorescence quenching of meso-tetrakis-4-sulfonatophenyl (TPPS(4)) and meso-tetrakis-4-N-methylpyridil (TMPyP) porphyrins is studied in aqueous solution and upon addition of micelles of sodium dodecylsulfate (SDS), cetyltrimethylammonium chloride (CTAC), N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (HPS) and t-octylphenoxypolyethoxyethanol (Triton X-100). Potassium iodide (KI) was used as quencher. Steady-state Stern-Volmer plots were best fitted by a quadratic equation, including dynamic (K(D)) and static (K(S)) quenching. K(S) was significantly smaller than K(D). Frequency-domain fluorescence lifetimes allowed estimating bimolecular quenching constants, k(q). At 25 degrees C, in aqueous solution, TMPyP shows k(q) values a factor of 2-3 higher than the diffusional limit. TPPS(4) shows collisional quenching with pH dependent k(q) values. For TMPyP quenching results are consistent with reported binding constants: a significant reduction of quenching takes place for SDS, a moderate reduction is observed for HPS and almost no change is seen for Triton X-100. Similar data were obtained at 50 degrees C. For CTAC-TPPS(4) system an enhancement of quenching was observed as compared to pure buffer. This is probably associated to accumulation of iodide at the cationic micellar interface. The attraction between CTAC headgroups and I(-), and repulsion between SDS and I(-), enhances and reduces the fluorescence quenching, respectively, of porphyrins located at the micellar interface. The small quenching of TPPS(4) in Triton X-100 is consistent with strong binding as reported in the literature.     

Adsorption of toluene, methylcyclohexane and neopentane on silica MCM-41

Adsorption-desorption isotherms of toluene, methylcyclohexane and neopentane were determined on a silica MCM-41 material of pore diameter ∼3.4 nm over the temperature range 258 K to 308 K (278 K for neopentane). The isosteric enthalpies of adsorption were determined from the isotherms at the various temperatures. It was found that the isotherms of toluene and methylcyclohexane have a similar variation with the temperature, exhibiting hysteresis at 268 K and at lower temperature, while the adsorption of neopentane is reversible at all temperatures. The three organic adsorptives interact differently with the silica surface and the isosteric enthalpies of adsorption indicated that methylcyclohexane has the weakest interaction and toluene the strongest. A slight increase in the adsorption enthalpy at the beginning of the capillary condensation step is observed with methylcyclohexane and neopentane but not with toluene.